CN116332580A - Preparation method for preparing simulated stone by using chrome-containing leather ash - Google Patents

Preparation method for preparing simulated stone by using chrome-containing leather ash Download PDF

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Publication number
CN116332580A
CN116332580A CN202310318178.XA CN202310318178A CN116332580A CN 116332580 A CN116332580 A CN 116332580A CN 202310318178 A CN202310318178 A CN 202310318178A CN 116332580 A CN116332580 A CN 116332580A
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China
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chrome
starch
agent
hours
parts
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段宝荣
张月
翁永根
曲家乐
秦静
李国荣
扈乐成
张彤
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Yantai University
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Yantai University
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    • E—FIXED CONSTRUCTIONS
    • E04—BUILDING
    • E04F—FINISHING WORK ON BUILDINGS, e.g. STAIRS, FLOORS
    • E04F13/00—Coverings or linings, e.g. for walls or ceilings
    • E04F13/07—Coverings or linings, e.g. for walls or ceilings composed of covering or lining elements; Sub-structures therefor; Fastening means therefor
    • E04F13/08—Coverings or linings, e.g. for walls or ceilings composed of covering or lining elements; Sub-structures therefor; Fastening means therefor composed of a plurality of similar covering or lining elements
    • E04F13/14—Coverings or linings, e.g. for walls or ceilings composed of covering or lining elements; Sub-structures therefor; Fastening means therefor composed of a plurality of similar covering or lining elements stone or stone-like materials, e.g. ceramics concrete; of glass or with an outer layer of stone or stone-like materials or glass
    • E04F13/147—Coverings or linings, e.g. for walls or ceilings composed of covering or lining elements; Sub-structures therefor; Fastening means therefor composed of a plurality of similar covering or lining elements stone or stone-like materials, e.g. ceramics concrete; of glass or with an outer layer of stone or stone-like materials or glass with an outer layer imitating natural stone, brick work or the like
    • C—CHEMISTRY; METALLURGY
    • C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
    • C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
    • C04B20/00—Use of materials as fillers for mortars, concrete or artificial stone according to more than one of groups C04B14/00 - C04B18/00 and characterised by shape or grain distribution; Treatment of materials according to more than one of the groups C04B14/00 - C04B18/00 specially adapted to enhance their filling properties in mortars, concrete or artificial stone; Expanding or defibrillating materials
    • C04B20/02—Treatment
    • C04B20/023—Chemical treatment
    • C—CHEMISTRY; METALLURGY
    • C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
    • C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
    • C04B24/00—Use of organic materials as active ingredients for mortars, concrete or artificial stone, e.g. plasticisers
    • C04B24/24—Macromolecular compounds
    • C04B24/38—Polysaccharides or derivatives thereof
    • C—CHEMISTRY; METALLURGY
    • C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
    • C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
    • C04B24/00—Use of organic materials as active ingredients for mortars, concrete or artificial stone, e.g. plasticisers
    • C04B24/40—Compounds containing silicon, titanium or zirconium or other organo-metallic compounds; Organo-clays; Organo-inorganic complexes
    • C04B24/42—Organo-silicon compounds
    • C—CHEMISTRY; METALLURGY
    • C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
    • C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
    • C04B26/00—Compositions of mortars, concrete or artificial stone, containing only organic binders, e.g. polymer or resin concrete
    • C—CHEMISTRY; METALLURGY
    • C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
    • C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
    • C04B28/00—Compositions of mortars, concrete or artificial stone, containing inorganic binders or the reaction product of an inorganic and an organic binder, e.g. polycarboxylate cements
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08B—POLYSACCHARIDES; DERIVATIVES THEREOF
    • C08B31/00—Preparation of derivatives of starch
    • C08B31/08—Ethers
    • C08B31/12—Ethers having alkyl or cycloalkyl radicals substituted by heteroatoms, e.g. hydroxyalkyl or carboxyalkyl starch
    • C08B31/125—Ethers having alkyl or cycloalkyl radicals substituted by heteroatoms, e.g. hydroxyalkyl or carboxyalkyl starch having a substituent containing at least one nitrogen atom, e.g. cationic starch
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F220/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical or a salt, anhydride ester, amide, imide or nitrile thereof
    • C08F220/02—Monocarboxylic acids having less than ten carbon atoms; Derivatives thereof
    • C08F220/52—Amides or imides
    • C08F220/54—Amides, e.g. N,N-dimethylacrylamide or N-isopropylacrylamide
    • C08F220/58—Amides, e.g. N,N-dimethylacrylamide or N-isopropylacrylamide containing oxygen in addition to the carbonamido oxygen, e.g. N-methylolacrylamide, N-(meth)acryloylmorpholine
    • C08F220/585—Amides, e.g. N,N-dimethylacrylamide or N-isopropylacrylamide containing oxygen in addition to the carbonamido oxygen, e.g. N-methylolacrylamide, N-(meth)acryloylmorpholine and containing other heteroatoms, e.g. 2-acrylamido-2-methylpropane sulfonic acid [AMPS]
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F8/00—Chemical modification by after-treatment
    • C08F8/44—Preparation of metal salts or ammonium salts
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G65/00—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule
    • C08G65/02—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule from cyclic ethers by opening of the heterocyclic ring
    • C08G65/32—Polymers modified by chemical after-treatment
    • C08G65/329—Polymers modified by chemical after-treatment with organic compounds
    • C08G65/331—Polymers modified by chemical after-treatment with organic compounds containing oxygen
    • C08G65/332—Polymers modified by chemical after-treatment with organic compounds containing oxygen containing carboxyl groups, or halides, or esters thereof
    • C08G65/3328—Polymers modified by chemical after-treatment with organic compounds containing oxygen containing carboxyl groups, or halides, or esters thereof heterocyclic
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G65/00—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule
    • C08G65/02—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule from cyclic ethers by opening of the heterocyclic ring
    • C08G65/32—Polymers modified by chemical after-treatment
    • C08G65/329—Polymers modified by chemical after-treatment with organic compounds
    • C08G65/333—Polymers modified by chemical after-treatment with organic compounds containing nitrogen
    • C08G65/33396—Polymers modified by chemical after-treatment with organic compounds containing nitrogen having oxygen in addition to nitrogen
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G65/00—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule
    • C08G65/02—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule from cyclic ethers by opening of the heterocyclic ring
    • C08G65/32—Polymers modified by chemical after-treatment
    • C08G65/329—Polymers modified by chemical after-treatment with organic compounds
    • C08G65/334—Polymers modified by chemical after-treatment with organic compounds containing sulfur
    • C08G65/3342—Polymers modified by chemical after-treatment with organic compounds containing sulfur having sulfur bound to carbon and hydrogen
    • C—CHEMISTRY; METALLURGY
    • C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
    • C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
    • C04B2103/00—Function or property of ingredients for mortars, concrete or artificial stone
    • C04B2103/60—Agents for protection against chemical, physical or biological attack
    • C04B2103/65—Water proofers or repellants
    • C—CHEMISTRY; METALLURGY
    • C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
    • C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
    • C04B2111/00—Mortars, concrete or artificial stone or mixtures to prepare them, characterised by specific function, property or use
    • C04B2111/00474—Uses not provided for elsewhere in C04B2111/00
    • C04B2111/00482—Coating or impregnation materials
    • C—CHEMISTRY; METALLURGY
    • C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
    • C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
    • C04B2111/00—Mortars, concrete or artificial stone or mixtures to prepare them, characterised by specific function, property or use
    • C04B2111/00474—Uses not provided for elsewhere in C04B2111/00
    • C04B2111/00612—Uses not provided for elsewhere in C04B2111/00 as one or more layers of a layered structure
    • C—CHEMISTRY; METALLURGY
    • C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
    • C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
    • C04B2111/00—Mortars, concrete or artificial stone or mixtures to prepare them, characterised by specific function, property or use
    • C04B2111/20—Resistance against chemical, physical or biological attack
    • C04B2111/2023—Resistance against alkali-aggregate reaction
    • C—CHEMISTRY; METALLURGY
    • C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
    • C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
    • C04B2111/00—Mortars, concrete or artificial stone or mixtures to prepare them, characterised by specific function, property or use
    • C04B2111/54—Substitutes for natural stone, artistic materials or the like
    • C04B2111/542—Artificial natural stone
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02W—CLIMATE CHANGE MITIGATION TECHNOLOGIES RELATED TO WASTEWATER TREATMENT OR WASTE MANAGEMENT
    • Y02W30/00—Technologies for solid waste management
    • Y02W30/50—Reuse, recycling or recovery technologies
    • Y02W30/91—Use of waste materials as fillers for mortars or concrete

Abstract

The preparation method of the simulated stone by using the chrome-containing leather ash comprises the steps of uniformly stirring the dried and modified chrome-containing leather ash, a cationic fixing agent and a starch waterproof agent, pouring the mixture into a mold, defoaming, and trowelling the surface; removing dust, grease, mould algae and other adherents on the painted surface, keeping the surface clean, dry and firm, and keeping the water content of the wall surface less than 10% and the pH value less than 10; leveling the wall surface by using matched plastering mortar, wherein the time is usually 2-3 times, scraping special putty powder, and polishing the surface, and cleaning floating dust; spraying, brushing and alkali-resistant sealing are carried out on the real stone surface, so that the base coating on the surface of the simulated stone is controlled to be about 1 mm, and the properties of the simulated stone are not reduced by adding chromium-containing chromium ash.

Description

Preparation method for preparing simulated stone by using chrome-containing leather ash
Technical Field
The invention relates to an application method of chrome-containing leather ash, in particular to a preparation method of chrome-containing leather ash for building simulation stone, which can prevent leakage of chrome ions.
Background
The invention is the first leather production country in the world, the total yield of leather is 9 hundred million square meters, and the leather is about one fourth of the world. Such high leather throughput creates 13000 billions of dollars per year and 889 billions of dollars in export, and also creates a huge amount of pollution to our environment. In addition to waste water pollution, pollution of solid waste is becoming an increasingly socioeconomic problem. The total amount of tanning waste is about 500 ten thousand tons worldwide, wherein the leather buffing ash is a type of protein solid waste containing chromium, synthetic grease, oil, tanning agent and dye generated in the leather production process. About 2kg-6kg of crust ash solid waste is produced per 1 ton of crust processed.
Chinese patent 2018102125052 provides a preparation method of functional refined leather ash synthetic leather powder, which comprises the following steps: (1) pretreatment of leather grinding ash; (2) preparation of hyperbranched polymer modified leather ash; (3) Blending with anion releasing agent to prepare functional refined leather ash. The powder for the wet coating of the synthetic leather, which is prepared by the method, enables the synthetic leather to have negative ion release, endogenous formaldehyde capture and excellent hygienic property. The main disadvantage is that the preparation cost is too high and the industrial application is difficult.
Characterization of asphalt cement for leather buffing ash modified flexible pavement (c.kamaraj1, thambiba sm.f2, siva Sankari P2, etc.) chinese leather, 2018, 47 (1): 35-41) discloses that BD (buff ash) containing chromium is used to make useful products, thereby reducing environmental pollution. A new asphalt was developed by mixing VG-30 asphalt, styrene-butadiene-styrene block copolymer (SBS), warm mix additive (Sasobit) and BD in the laboratory. Ultra high grade (Super pavement) asphalt cement testing, rotational viscometer, and Dynamic Shear Rheometer (DSR) were used to test Performance Grading (PG), the test procedure followed standard ASTM D6373, and the new asphalt cement was designated PG-88. Physicochemical properties such as FT-IR, DSC/TGA, SEM/EDAX, rheological properties and aging were evaluated. From DSR values, PG 88 has better fatigue (G.sin delta) and rut resistance (G.sin delta), and can be used as an alternative asphalt for asphalt pavement. The main disadvantage is that the leather ash is limited by market capacity, the use amount of the leather ash is too small, and the leather ash cannot be used as a main choice for recycling waste.
The team issued Chinese patent ZL 2019108571085 provides a method for manufacturing a particle board by using chrome-containing leather grinding ash, wherein the processed chrome-containing leather grinding ash, glue, nitrogen-phosphorus flame retardant, toughening agent, toughening synergist, flame-retardant synthetic fatliquor, substance B and water-based transparent waterproof agent are uniformly mixed, placed into a die, heated and pressurized in a flat vulcanizing machine, sprayed with substance C and isopropyl palmitate on the surface, and cured to obtain the particle board. The obtained particle board has good flame retardance, wear resistance and dye stability. The invention adopts a physical-chemical combination mode to use leather scraps as particle boards on the basis of not damaging leather ash materials, but the particle boards have unsmooth surfaces and long surfaces, are easy to remove slag due to friction, and are easy to popularize and limited.
The team ZL2021103860777 relates to a preparation method of foam concrete based on utilization of tanning chrome-containing leather scraps and coal gangue, and the foam concrete is prepared by adopting the processes of leather scraps hydrolysis, rosin acyl chloride modified leather scraps hydrolysate preparation, compounding and coal gangue foaming treatment. The invention has the comprehensive advantages that the leather scraps and the coal gangue are completely exhausted, no secondary pollution is caused, the purpose of recycling waste is achieved, the invention belongs to the hydrolysis damage to the chrome-containing leather scraps, and relatively speaking, the hydrolysis process belongs to the stage with the highest cost of recycling waste from the aspects of energy consumption and cost, so that the invention is particularly important to find a waste treatment mode with more cost saving.
From real estate to infrastructure, from domestic to foreign, from one domain to the whole domain, from EPC to PPP, from a single enterprise to an industrial town, from sales to self-contained properties, the building industry is moving to multiple industries, multi-domain transfer, and more business development.
The chromium-containing leather ash is used for the wall surface of a building, the chromium-containing leather ash can be consumed in a large amount in the field, and the main problem solved by the leather ash in the field is that chromium ions and dyes can be fixed and cannot leak to the outside under the condition of long-time rainwater soaking and sunlight irradiation, and meanwhile, a large amount of hexavalent chromium ions cannot be generated after the sunlight is irradiated for a long time.
At present, the research technology of using chrome-containing leather ash for building wall surfaces is not reported, the team is devoted to the combined attack of the difficult problem of the chrome-containing leather ash, which puzzles a tanning enterprise, on the research basis of chrome-containing leather scraps for a long time since 2006, so as to find a new channel for the application of the chrome-containing leather ash, and the reason that the traditional chrome-containing leather ash is difficult to research by everybody is that the chrome-containing leather ash is subjected to chemical hydrolysis treatment, and a large amount of dye contained in the chrome-containing leather ash is difficult to remove color and high in cost, so that the chrome-containing leather ash is a traditional college of leather profession: the university of Sichuan, the university of Shaanxi and the university of Qilu industry have few researches on the problem, so the team uses the chrome-containing leather ash to the building wall based on the double basis of chemistry and civil engineering, and is expected to find a reasonable method, thereby providing a new channel for recycling the leather ash.
Disclosure of Invention
The invention fixes chromium ion in chromium-containing leather ash, adds 12-18% chromium-containing leather ash in cement, uses cation fixing agent and starch waterproof agent to fix free chromium complex, uses starch waterproof agent to avoid or reduce contact of water and chromium-containing leather ash, and adopts compatilizer to improve compatibility of part of leather scraps in simulated stone surface and alkali-resistant seal primer, and protect stability of primer.
The preparation method for preparing the simulated stone by using the chrome-containing leather ash is characterized by comprising the following steps: the composition comprises cement, calcium chloride, modified chrome-containing leather grinding ash, ethylhexyl palmitate, tertiary glycidyl carbonate, a cation fixing agent, a starch waterproofing agent and a priming paint for alkali-resistant seal; the preparation method of the modified chrome-containing leather ash comprises the following steps: 100g of chrome-containing leather grinding ash is crushed into millimeter size, then is uniformly mixed with 2-4 g of oxalic acid and 120-130 g of water, is stirred and adjusted to pH 4-4.5, 0.3-2.1 g of sodium citrate dihydrate and 3-6 g of chrome fixing agent are added, stirring is carried out for 2 hours at 45 ℃, and after continuous stirring, the modified chrome-containing leather ash is obtained; the preparation method of the chromium fixing agent comprises the following steps: 20g of 2-acrylamide-2-methylpropanesulfonic acid, 12-15 g of acetoacetic acid ethyl ester and 10g of water are stirred and dispersed at 50-60 ℃, 12-25 g of methacryloxyethyl trimethyl ammonium chloride, 0.6-0.9 g of ethylenediamine tetraacetic acid and 400-500 g of water are sequentially added, 2.25-2.7 g of potassium persulfate initiator is added, stirring and reacting for 1-2h at 70-80 ℃, 1.6-2.7 g of aluminum hydroxy oxalate is added, the pH value is regulated to 7.5, the reaction is carried out for 1-2h under heat preservation, and the chromium fixing agent is obtained through vacuum drying.
The preparation method for preparing the simulated stone by using the chrome-containing leather ash comprises the following steps:
(1) Uniformly stirring 42.5-grade cement, calcium chloride, ethylhexyl palmitate, versatic acid glycidyl ester, and the dried modified chrome-containing leather ash obtained by the method in claim 1, wherein the weight ratio of the modified chrome-containing leather ash, the 42.5-grade cement, the calcium chloride, the ethylhexyl palmitate, the versatic acid glycidyl ester, the cationic fixing agent, the starch waterproof agent and the water is as follows: 100: (595-775): (3-8): (1-2): (2-3): (1-2): (2-3): (800-1000), continuing stirring, pouring into a mold, defoaming, and trowelling the surface;
(2) And (3) treating a base material: removing dust, grease, mould algae and other adherents on the painted surface, keeping the surface clean, dry and firm, and keeping the water content of the wall surface less than 10% and the pH value less than 10;
(3) Leveling the wall surface: leveling the wall surface by using matched plastering mortar, wherein the time is usually 2-3 times, scraping special putty powder, and polishing the surface, and cleaning floating dust;
(4) Spraying the true stone surface in the step (3), and brushing with alkali-resistant seal to make the base coat on the simulated stone surface be controlled at 1 mm;
the alkali-resistant seal primer comprises the following components: 180 parts of water, 0.6 part of hydroxyethyl cellulose (the hydroxyethyl cellulose of Shi lan 250HBR, the same applies hereinafter) and 16 parts of HYM-21 rubber powder (Beijing Cyclo Yimei HYM-21 plant rubber powder, the same applies hereinafter); 4 parts of propylene glycol; 0.7 parts of wetting agent (German Konning PE-100, hereinafter); 2.7 parts of dispersant (5040 in taiwan, hereinafter the same); 2 parts of an antifoaming agent (Japanese nopraceae NXZ, hereinafter); 3 parts of multifunctional auxiliary agent (Amp-95, the same applies below); 38 parts of titanium dioxide (996 of Sichuan python, the same applies below); 63 parts of other fillers (heavy calcium 1000 mesh, henan eastern calcium Co., ltd., hereinafter the same); 50 parts of quartz sand (120 meshes) (Hebei Lingshou county Hecheng color sand factory); 13 parts of film forming aid (Tschmann alcohol ester twelve film forming aid, hereinafter); bade Fu RS-308260 parts (Guangdong Bade Fu technology Co., ltd.); 0.3 part of penetrating agent (penetrating agent JFC-M (Jiangsu sea-Ann petrochemical plant), 0.4-5 parts of alkali swelling thickener (Nantong city Tai chemical industry Co., ltd.) and 10-20 parts of compatilizer;
the preparation method of the compatilizer comprises the following steps: 16g of cardanol polyoxyethylene ether BGF-6 (Shanghai high chemical Co., ltd.) and 15g of 1, 4-butanedithiol are stirred and reacted for 1-2 hours at 70-80 ℃, 1, 4-butanedithiol is removed at 40 ℃ after cooling, 6-8 g of DL-panthenol is added and reacted for 30-60 minutes at 45 ℃, 6-7 g of o-cresolphthalide is added and reacted for 1-2 hours at 45 ℃, and the pH value is regulated to 7.5, so that the compatilizer is obtained.
The cation fixing agent is as follows: a, heating and stirring high-amylose corn starch milk (mass fraction of 35%, pH value of 6.5 and the rest of water) for 20 hours at 65 ℃, then adding propylene oxide with starch content of 30% in 2 times, and adding NaOH (2.5% of dry weight of starch) and Na 2 SO 4 (20% of water), reacting at 45 ℃ for 24 hours, neutralizing, filtering, washing and drying to obtain hydroxypropyl starch;
b preparing 350mL of acetate buffer solution (the rest is water) by using 25.6g of anhydrous sodium acetate and 11.2mL of acetic acid, dissolving 15g of hydroxypropyl starch in the acetate buffer solution at 60 ℃, adding 1.3mL of propargylamine under stirring, adding sodium cyanoborohydride for 4 times, each time 0.3g, stirring the mixture at 50 ℃ for 12 hours, dialyzing for 24 hours, concentrating the solution by a rotary evaporator after dialysis, and drying in vacuum for 24 hours to obtain the terminal alkyne starch; 20mL of N, N-dimethylformamide was mixed with 40mL of water, 6g of terminal alkyne starch and 260mg of 3-azidopropylamine were dissolved in the above mixed solution, 45mg of copper sulfate pentahydrate and 45mg of sodium ascorbate were added, and the solution was stirred at 80℃for 12 hours, the above product was dissolved in a mixture of 20mL of methylene chloride and 20mL of trifluoroacetic acid, and deprotected (in N-pass 2 Stirring at room temperature for 6h under the condition, and then dialyzing the solution for 48h and drying to obtain the terminal cationic starch.
Starch waterproof agent: respectively weighing 16g of hydroxypropyl starch and 14-17 g of terminal cationic starch in the claim (4), preparing a suspension with the concentration of 6% by deionized water, and placing the suspension in a three-neck flask; mechanically stirring, heating and preserving heat for 2 hours in a constant-temperature water bath at 98 ℃ to obtain membrane liquid; 3g of hydroxyl silicone oil (the mass ratio of the curing agent is 15:1) is dissolved in 50mL of ethyl acetate to be mixed with the film liquid, the mixture is stirred and reacted for 1 to 2 hours at the temperature of 70 to 80 ℃, then 6g of water, 3 to 4g of coupling agent and 0.3 to 0.5g of 1- (3-chloropropoxy) -4-fluorobenzene are added, the pH value is adjusted to 10, the mixture is stirred and reacted for 1 to 2 hours at the temperature of 30 to 40 ℃, and the mixture is dried in vacuum to obtain the starch waterproof agent.
The coupling agents are KH550 and KH570.
The invention has the advantages that:
(1) Because most of chromium ions and carboxyl groups of leather are in single-point combination in tanning, the ratio of multi-point combination is low, the stability of single-point combination is poor, a lot of single-point combination chromium ions can migrate out after water, 201910857108.5 (the early achievement of the team) adopts oxalic acid to carry out proper tanning on leather grinding dust, the obtained chromium-containing chromium liquid concentrate is used as a tanning agent, free chromium ions in leather dust are reduced through the tanning, the 201910857108.5 method is mainly used for indoor floors, the environment used by the method is outdoor again, the influence of rainwater on the chromium ion migration is large, the chromium ion fixing agent substance A is modified on the basis of early study of a subject group, the single-point combination chromium ion fixing is increased, the residual chromium ions in the leather dust are respectively fixed and dye are respectively fixed by adopting sodium citrate dihydrate and a chromium fixing agent, the migration of the subsequent chromium ions and dye is reduced, the surface of the leather dust is fixed in advance by adopting a starch waterproof agent, and the chromium ion migration can be prevented. (2) The chromium fixation has the advantages that 2-acrylamide-2-methylpropanesulfonic acid is dispersed in a system of acetoacetic acid ethyl ester and water, methacryloxyethyl trimethyl ammonium chloride is added, potassium persulfate is used as an initiator to carry out free radical addition reaction, then imine group in 2-acrylamide-2-methylpropanesulfonic acid is reacted with ethylenediamine tetraacetic acid, ethylenediamine tetraacetic acid is introduced into a polymer chain, then aluminum hydroxy oxalate reacts with carboxylic acid of hydroxy sulfonate and ethylenediamine tetraacetic acid in a weak alkaline environment, and the ethylenediamine tetraacetic acid and the aluminum hydroxy oxalate with strong complexing capacity are connected to a molecular chain, so that chromium fixation and chromium complex adsorption are facilitated, deposition in leather ash is facilitated, and the fixation of chromium is facilitated.
(3) The invention designs a method for preparing terminal cationic starch, which can fix chromium in chromium complex in chrome leather ash, and is beneficial to fixing chromium if free chromium is biased negative.
(4) The preparation method comprises the steps of carrying out hydroxypropylation modification on high amylose starch to obtain hydroxypropyl modified starch, introducing alkynyl at the unique reducing end of the starch, grafting cations at the end through the 'click' reaction of azide and alkyne to obtain a starch molecular chain with positive charges at the end, orienting the starch molecular chain in the film forming process under the action of an external electric field, carrying out hydrophobic modification on an oriented starch film by utilizing hydroxyl silicone oil, hydrolyzing the oriented starch film by adopting a coupling agent and water under a certain pH environment, and polymerizing the hydrolysis product of the coupling agent by utilizing redundant hydroxyl silicone oil, thereby improving the waterproofness of the starch, and simultaneously delaying the reaction rate of the hydrolysis product of the coupling agent and the polyhydroxy silicone oil by using 1- (3-chloropropoxy) -4-fluorobenzene so as to prevent the reaction rate of the hydrolysis product of the coupling agent from being controllable and not seriously exploded.
(5) The invention adopts double bond contained in cardanol polyoxyethylene ether and two hydrogen in 1, 4-butanedithiol to carry out addition under the reheating environment to generate an intermediate of terminal hydroxyl and thiol, then adopts polyhydroxy DL-panthenol to modify the intermediate, reacts with thiol, then adopts o-creosote with stronger complexing ability to chromium to react with hydroxyl of DL-panthenol, finally adjusts pH to 7.5, controls phenolic hydroxyl in the o-creosote to be in salt environment, is convenient for complexing the obtained compatilizer with free chromium ions or combining with chromium complex, protein carboxyl and amino in the leather ash, so that the cement, the leather ash and the primer achieve the compatible effect, and simultaneously, the free chromium ions are properly fixed.
(6) Aluminum hydroxy oxalate was obtained from example 1 of patent 200410000109.1, and the present invention relates to a raw material which does not indicate the enterprise, and the main and core raw materials can achieve the above functions.
Detailed Description
Example one
The preparation method of the modified chrome-containing leather ash comprises the following steps: crushing 100g of chrome-containing leather grinding ash to millimeter size, uniformly mixing with 2g of oxalic acid and 120g of water, stirring, adjusting the pH to 4-4.5, adding 0.3g of sodium citrate dihydrate and 3g of chrome fixing agent, stirring at 45 ℃ for 2 hours, continuously stirring, and drying to obtain modified chrome-containing leather ash; the preparation method of the chromium fixing agent comprises the following steps: stirring and dispersing 20g of 2-acrylamide-2-methylpropanesulfonic acid, 12g of ethyl acetoacetate and 10g of water at 50 ℃, sequentially adding 12g of methacryloxyethyl trimethyl ammonium chloride, 0.6g of ethylenediamine tetraacetic acid and 400g of water, adding 2.25g of potassium persulfate initiator (10 g of water is dissolved, the same applies below), stirring and reacting for 1h at 70 ℃, then adding 1.6g of aluminum hydroxy oxalate, regulating the pH value to 7.5, carrying out heat preservation and reacting for 1h, and carrying out vacuum drying to obtain the chromium fixing agent.
The preparation method for preparing the simulated stone by using the chrome-containing leather ash comprises the following steps:
(1) Uniformly stirring 42.5-grade cement, calcium chloride, ethylhexyl palmitate, versatic acid glycidyl ester, and the dried modified chrome-containing leather ash obtained by the method in claim 1, wherein the weight ratio of the modified chrome-containing leather ash, the 42.5-grade cement, the calcium chloride, the ethylhexyl palmitate, the versatic acid glycidyl ester, the cationic fixing agent, the starch waterproof agent and the water is as follows: 100:595:3:1:2:1:2:800, continuing stirring, pouring into a mold, defoaming, and trowelling the surface;
(2) And (3) treating a base material: removing dust, grease, mould algae and other adherents on the painted surface, keeping the surface clean, dry and firm, and keeping the water content of the wall surface less than 10% and the pH value less than 10;
(3) Leveling the wall surface: leveling the wall surface by using matched plastering mortar, wherein the time is usually 2-3 times, scraping special putty powder, and polishing the surface, and cleaning floating dust;
(4) Spraying the true stone surface in the step (3), and brushing with alkali-resistant seal to make the base coat on the simulated stone surface be controlled at 1 mm;
the alkali-resistant seal primer comprises the following components: 180 parts of water, 0.6 part of hydroxyethyl cellulose (the hydroxyethyl cellulose of Shi lan 250HBR, the same applies hereinafter) and 16 parts of HYM-21 rubber powder (Beijing Cyclo Yimei HYM-21 plant rubber powder, the same applies hereinafter); 4 parts of propylene glycol; 0.7 parts of wetting agent (German Konning PE-100, hereinafter); 2.7 parts of dispersant (5040 in taiwan, hereinafter the same); 2 parts of an antifoaming agent (Japanese nopraceae NXZ, hereinafter); 3 parts of multifunctional auxiliary agent (Amp-95, the same applies below); 38 parts of titanium dioxide (996 of Sichuan python, the same applies below); 63 parts of other fillers (heavy calcium 1000 mesh, henan eastern calcium Co., ltd., hereinafter the same); 50 parts of quartz sand (120 meshes, hebei Lingshou county Hecheng color sand factory); 13 parts of film forming aid (Tschmann alcohol ester twelve film forming aid, hereinafter); bade Fu RS-308260 parts (Guangdong Bade Fu technology Co., ltd.); 0.3 part of penetrating agent (penetrating agent JFC-M (sea-safe petrochemical plant of Jiangsu province), 0.4 part of alkali swelling thickener (thickener 935 of Tai chemical industry Co., ltd.) of Nantong, and 10 parts of compatilizer;
the preparation method of the compatilizer comprises the following steps: 16g of cardanol polyoxyethylene ether BGF-6 (Shanghai high chemical Co., ltd.) and 15g of 1, 4-butanedithiol are stirred and reacted for 1h at 70 ℃, then DL-panthenol 6.8 g is added at 40 ℃ and reacted for 30min at 45 ℃, then o-cresolphthalein 6g is added and reacted for 1h at 45 ℃, and the pH is regulated to 7.5, thus obtaining the compatilizer.
The cation fixing agent is as follows: a, heating and stirring high-amylose corn starch milk (mass fraction of 35%, pH value of 6.5 and the rest of water) for 20 hours at 65 ℃, then adding propylene oxide with starch content of 30% in 2 times, and adding NaOH (2.5% of dry weight of starch) and Na 2 SO 4 (20% of water), reacting at 45 ℃ for 24 hours, neutralizing, filtering, washing and drying to obtain hydroxypropyl starch;
b preparing 350mL of acetate buffer solution (the rest is water) by using 25.6g of anhydrous sodium acetate and 11.2mL of acetic acid, dissolving 15g of hydroxypropyl starch in the acetate buffer solution at 60 ℃, adding 1.3mL of propargylamine under stirring, adding 0.3g of sodium cyanoborohydride each time, 1h each time interval and 12h of reaction (the same applies below), stirring the mixture at 50 ℃ for 32h, dialyzing for 24h, concentrating the solution by a rotary evaporator after dialysis, and vacuum drying for 24h to obtain the terminal alkyne starch; 20mL of N, N-dimethylformamide was mixed with 40mL of water, 6g of terminal alkyne starch and 260mg of 3-azidopropylamine were then dissolved in the above mixed solution, 45mg of copper sulfate pentahydrate and 45mg of sodium ascorbate were added, and the solution was stirred at 80℃for 12 hours, and the above product was dissolved in 20mL of methylene chloride and 20mL of trifluoroethyl fluorideDeprotection in acid mixture (under N-pass 2 Stirring at room temperature for 6h under the condition, and then dialyzing the solution for 48h and drying to obtain the terminal cationic starch.
Starch waterproof agent: respectively weighing 16g of hydroxypropyl starch and 14g of terminal cationic starch, preparing a suspension with the concentration of 6% by deionized water, and placing the suspension in a three-neck flask; mechanically stirring, heating and preserving heat for 2 hours in a constant-temperature water bath at 98 ℃ to obtain membrane liquid; 3g of hydroxyl silicone oil (the mass ratio of the diethylenetriamine curing agent is 15:1, the curing agent is small, the following is the same) is dissolved in 50mL of ethyl acetate to neutralize the membrane solution, the mixture is mixed and reacted for 1h at 70 ℃, then 6g of water, 3g of coupling agent KH550 and 0.3g of 1- (3-chloropropoxy) -4-fluorobenzene are added, the pH is adjusted to be 10, the mixture is stirred and reacted for 1h at 30 ℃, and the mixture is dried in vacuum to obtain the starch waterproof agent.
Example two
The preparation method of the modified chrome-containing leather ash comprises the following steps: 100g of chrome-containing leather grinding ash is crushed into millimeter size, then evenly mixed with 4g of oxalic acid and 130g of water, stirred and adjusted to pH 4-4.5, added with 2.1g of sodium citrate dihydrate and 6g of chrome fixing agent, stirred for 2 hours at 45 ℃, continuously stirred and dried to obtain modified chrome-containing leather ash; the preparation method of the chromium fixing agent comprises the following steps: stirring and dispersing 20g of 2-acrylamide-2-methylpropanesulfonic acid, 15g of ethyl acetoacetate and 10g of water at 60 ℃, sequentially adding 25g of methacryloxyethyl trimethyl ammonium chloride, 0.9g of ethylenediamine tetraacetic acid and 500g of water, adding 2.7g of potassium persulfate initiator, stirring and reacting for 2 hours at 80 ℃, then adding 2.7g of aluminum hydroxy oxalate, regulating the pH value to 7.5, reacting for 2 hours at the temperature of heat preservation, and vacuum drying to obtain the chromium fixing agent.
The preparation method for preparing the simulated stone by using the chrome-containing leather ash comprises the following steps:
(1) The modified chrome-containing leather ash, 42.5-grade cement, calcium chloride, ethylhexyl palmitate, tertiary glycidyl carbonate, a cation fixing agent, a starch waterproof agent and water are prepared according to the following weight proportion: 100:775:8:2:3:2:3:1000, stirring uniformly, pouring into a mold, defoaming, and trowelling the surface;
(2) And (3) treating a base material: removing dust, grease, mould algae and other adherents on the painted surface, keeping the surface clean, dry and firm, and keeping the water content of the wall surface less than 10% and the pH value less than 10;
(3) Leveling the wall surface: leveling the wall surface by using matched plastering mortar, wherein the time is usually 2-3 times, scraping special putty powder, and polishing the surface, and cleaning floating dust;
(4) Spraying the true stone surface in the step (3), and brushing with alkali-resistant seal to make the base coat on the simulated stone surface be controlled at 1 mm;
the alkali-resistant seal primer comprises the following components: 180 parts of water, 0.6 part of hydroxyethyl cellulose (the hydroxyethyl cellulose of Shi lan 250HBR, the same applies hereinafter) and 16 parts of HYM-21 rubber powder (Beijing Cyclo Yimei HYM-21 plant rubber powder, the same applies hereinafter); 4 parts of propylene glycol; 0.7 parts of wetting agent (German Konning PE-100, hereinafter); 2.7 parts of dispersant (5040 in taiwan, hereinafter the same); 2 parts of an antifoaming agent (Japanese nopraceae NXZ, hereinafter); 3 parts of multifunctional auxiliary agent (Amp-95, the same applies below); 38 parts of titanium dioxide (996 of Sichuan python, the same applies below); 63 parts of other fillers (heavy calcium 1000 mesh, henan eastern calcium Co., ltd., hereinafter the same); 50 parts of quartz sand (120 meshes) (Hebei Lingshou county Hecheng color sand factory); 13 parts of film forming aid (Tschmann alcohol ester twelve film forming aid, hereinafter); bade Fu RS-308260 parts (Guangdong Bade Fu technology Co., ltd.); 0.3 part of penetrating agent (penetrating agent JFC-M (petrochemical plant of sea-safe in Jiangsu province), 5 parts of alkali swelling thickener (thickener 935 of Tai chemical industry Co., ltd., nantong Co., ltd.), and 20 parts of compatilizer;
the preparation method of the compatilizer comprises the following steps: 16g of cardanol polyoxyethylene ether BGF-6 (Shanghai high chemical Co., ltd.) and 15g of 1, 4-butanedithiol are stirred and reacted for 2 hours at 80 ℃, then 6.8g of DL-panthenol is added at 40 ℃ and reacted for 60 minutes at 45 ℃, then 7g of o-cresolphthalein is added and reacted for 2 hours at 45 ℃, and the pH value is regulated to 7.5, so that the compatilizer is obtained.
The cation fixing agent is as follows: a, heating and stirring high-amylose corn starch milk (mass fraction of 35%, pH value of 6.5 and the rest of water) for 20 hours at 65 ℃, then adding propylene oxide with starch content of 30% in 2 times, and adding NaOH (2.5% of dry weight of starch) and Na 2 SO 4 (20% of water), reacting at 45 ℃ for 24 hours, neutralizing, filtering, washing and drying to obtain hydroxypropyl starch;
b preparing 350mL of acetate buffer solution (the rest is water) by using 25.6g of anhydrous sodium acetate and 11.2mL of acetic acid, dissolving 15g of hydroxypropyl starch in the acetate buffer solution at 60 ℃, adding 1.3mL of propargylamine under stirring, adding 0.3g of sodium cyanoborohydride each time, 1h each time interval and 12h of reaction (the same applies below), stirring the mixture at 50 ℃ for 32h, dialyzing for 24h, concentrating the solution by a rotary evaporator after dialysis, and drying in vacuum for 24h to obtain the terminal alkyne starch; 20mL of N, N-dimethylformamide was mixed with 40mL of water, 6g of terminal alkyne starch and 260mg of 3-azidopropylamine were dissolved in the above mixed solution, 45mg of copper sulfate pentahydrate and 45mg of sodium ascorbate were added, and the solution was stirred at 80℃for 12 hours, the above product was dissolved in a mixture of 20mL of methylene chloride and 20mL of trifluoroacetic acid, and deprotected (in N-pass 2 Stirring at room temperature for 6h under the condition, and then dialyzing the solution for 48h and drying to obtain the terminal cationic starch.
Starch waterproof agent: respectively weighing 16g of the prepared hydroxypropyl starch and 17g of the terminal cationic starch, preparing a suspension with the concentration of 6% by using deionized water, and placing the suspension into a three-neck flask; mechanically stirring, heating and preserving heat for 2 hours in a constant-temperature water bath at 98 ℃ to obtain membrane liquid; 3g of hydroxyl silicone oil (the mass ratio of the diethylenetriamine curing agent is 15:1, the curing agent is small, the following is the same) is dissolved in 50mL of ethyl acetate to neutralize the membrane solution, the mixture is stirred and reacted for 2 hours at 80 ℃, then 6g of water, 4g of KH570 coupling agent and 0.5g of 1- (3-chloropropoxy) -4-fluorobenzene are added, the pH is adjusted to be 10, the mixture is stirred and reacted for 2 hours at 40 ℃, and the mixture is dried in vacuum to obtain the starch waterproof agent.
Example three
The preparation method of the modified chrome-containing leather ash comprises the following steps: 100g of chrome-containing leather grinding ash is crushed into millimeter size, then evenly mixed with 3g of oxalic acid and 125g of water, stirred and adjusted to pH 4-4.5, 1.2g of sodium citrate dihydrate and 4.5g of chrome fixing agent are added, stirred for 2 hours at 45 ℃, and dried after continuous stirring, thus obtaining modified chrome-containing leather ash;
the preparation method of the chromium fixing agent comprises the following steps: 20g of 2-acrylamide-2-methylpropanesulfonic acid, 13.5g of ethyl acetoacetate and 10g of water are stirred and dispersed at 55 ℃, 18.5g of methacryloxyethyl trimethyl ammonium chloride, 0.75g of ethylenediamine tetraacetic acid and 450g of water are sequentially added, 2.5g of potassium persulfate initiator is added, stirring reaction is carried out for 1.5h at 75 ℃, then 2.1g of aluminum hydroxy oxalate is added, the pH value is regulated to 7.5, the reaction is carried out for 1.5h under heat preservation, and the chromium fixing agent is obtained through vacuum drying.
The preparation method for preparing the simulated stone by using the chrome-containing leather ash comprises the following steps:
(1) The modified chrome leather ash, 42.5-grade cement, calcium chloride, ethylhexyl palmitate, tertiary glycidyl carbonate, a cation fixing agent, a starch waterproof agent and water are mixed according to the weight ratio: 100:680:5.5:1.5:2.5:1.5:2.5:900, stirring uniformly, pouring into a mold, defoaming, and trowelling the surface;
(2) And (3) treating a base material: removing dust, grease, mould algae and other adherents on the painted surface, keeping the surface clean, dry and firm, and keeping the water content of the wall surface less than 10% and the pH value less than 10;
(3) Leveling the wall surface: leveling the wall surface by using matched plastering mortar, wherein the time is usually 2-3 times, scraping special putty powder, and polishing the surface, and cleaning floating dust;
(4) Spraying the true stone surface in the step (3), and brushing with alkali-resistant seal to make the base coat on the simulated stone surface be controlled at 1 mm;
the alkali-resistant seal primer comprises the following components: 180 parts of water, 0.6 part of hydroxyethyl cellulose (the hydroxyethyl cellulose of Shi lan 250HBR, the same applies hereinafter) and 16 parts of HYM-21 rubber powder (Beijing Cyclo Yimei HYM-21 plant rubber powder, the same applies hereinafter); 4 parts of propylene glycol; 0.7 parts of wetting agent (German Konning PE-100, hereinafter); 2.7 parts of dispersant (5040 in taiwan, hereinafter the same); 2 parts of an antifoaming agent (Japanese nopraceae NXZ, hereinafter); 3 parts of multifunctional auxiliary agent (Amp-95, the same applies below); 38 parts of titanium dioxide (996 of Sichuan python, the same applies below); 63 parts of other fillers (heavy calcium 1000 mesh, henan eastern calcium Co., ltd., hereinafter the same); 50 parts of quartz sand (120 meshes) (Hebei Lingshou county Hecheng color sand factory); 13 parts of film forming aid (Tschmann alcohol ester twelve film forming aid, hereinafter); bade Fu RS-308260 parts (Guangdong Bade Fu technology Co., ltd.); 0.3 part of penetrating agent (penetrating agent JFC-M (sea-safe petrochemical plant of Jiangsu province), 2.7 parts of alkali swelling thickener (thickener 935 of Tai chemical industry Co., ltd.) of Nantong, and 15 parts of compatilizer;
the preparation method of the compatilizer comprises the following steps: 16g of cardanol polyoxyethylene ether BGF-6 (Shanghai high chemical Co., ltd.) and 15g of 1, 4-butanedithiol are stirred and reacted for 1.5h at 75 ℃, then DL-panthenol 6.8 g is added at 40 ℃ and reacted for 45min at 45 ℃, then o-cresolphthalein 6.5g is added and reacted for 1.5h at 45 ℃, and the pH value is regulated to 7.5, thus obtaining the compatilizer.
The cation fixing agent is as follows: a, heating and stirring high-amylose corn starch milk (mass fraction of 35%, pH value of 6.5 and the rest of water) for 20 hours at 65 ℃, then adding propylene oxide with starch content of 30% in 2 times, and adding NaOH (2.5% of dry weight of starch) and Na 2 SO 4 (20% of water), reacting at 45 ℃ for 24 hours, neutralizing, filtering, washing and drying to obtain hydroxypropyl starch;
b preparing 350mL of acetate buffer solution (the rest is water) by using 25.6g of anhydrous sodium acetate and 11.2mL of acetic acid, dissolving 15g of hydroxypropyl starch in the acetate buffer solution at 60 ℃, adding 1.3mL of propargylamine under stirring, adding 0.3g of sodium cyanoborohydride each time, 1h each time interval and 12h of reaction (the same applies below), stirring the mixture at 50 ℃ for 32h, dialyzing for 24h, concentrating the solution by a rotary evaporator after dialysis, and drying in vacuum for 24h to obtain the terminal alkyne starch; 20mL of N, N-dimethylformamide was mixed with 40mL of water, 6g of terminal alkyne starch and 260mg of 3-azidopropylamine were dissolved in the above mixed solution, 45mg of copper sulfate pentahydrate and 45mg of sodium ascorbate were added, and the solution was stirred at 80℃for 12 hours, the above product was dissolved in a mixture of 20mL of methylene chloride and 20mL of trifluoroacetic acid, and deprotected (in N-pass 2 Stirring at room temperature for 6h under the condition, and then dialyzing the solution for 48h and drying to obtain the terminal cationic starch.
Starch waterproof agent: preparing suspension with concentration of 6% by deionized water from 16g of hydroxypropyl starch and 15.5g of terminal cationic starch respectively, and placing the suspension into a three-neck flask; mechanically stirring, heating and preserving heat for 2 hours in a constant-temperature water bath at 98 ℃ to obtain membrane liquid; 3g of hydroxy silicone oil (the mass ratio of the diethylenetriamine curing agent is 15:1, the curing agent dosage is less, the following is the same) is dissolved in 50mL of ethyl acetate to neutralize the membrane solution, the mixture is mixed and reacted for 1.5 hours at the temperature of 75 ℃, then 6g of water, 3.5g of KH550 coupling agent and 0.4g of 1- (3-chloropropoxy) -4-fluorobenzene are added, the pH is adjusted to be 10, the mixture is stirred and reacted for 1.5 hours at the temperature of 35 ℃, and the mixture is dried in vacuum to obtain the starch waterproof agent.
The peel strength is measured and controlled by a field precision HTS-BLY2510 full-computer peel strength tester.
TABLE 1 Peel Strength of primer
Figure BDA0004150740020000181
Comparative example the real stone paint of example one of 2019110496650 was used to simulate the stone surface and retested in the same environment (as opposed to its experimental data), and from the peel strength of the primer in table 1 it was found that the compatibilizing agent, o-cresolphthalein, DL-panthenol exert an effect of improving the compatibility of the primer with the simulated stone surface.
The prepared simulated stone was immersed in 100ml of water for 96 hours, and the cr concentration was measured using an atomic absorption meter.
TABLE 2 chromium ion concentration
Figure BDA0004150740020000191
From Table 2, it was found that chromium fixing agent, aluminum hydroxy oxalate, ethylenediamine tetraacetic acid, cationic fixing agent and starch waterproofing agent all had an effect on the concentration of chromium ions for washing with water, and experiments found that this method was carried out on a true stone surface irradiated with sunlight for 96 hours, immersed in water for 96 hours, and no hexavalent chromium at ppm level was found to appear.
Compressive strength was tested according to JC 79-92 natural marble building board and GB/T9966.1-2020 natural stone test method; the thickness of the sample was controlled at 50mm.
TABLE 3 compressive strength
Figure BDA0004150740020000201
It can be found from Table 3 that the addition of the modified chromium ash reduces the compressive strength of the real stone, but the reduction is controllable, so that the standard requirement of JC 79-92 natural marble building board exceeding 20Mpa can be met.

Claims (6)

1. The preparation method for preparing the simulated stone by using the chrome-containing leather ash is characterized by comprising the following steps: the composition comprises cement, calcium chloride, modified chrome-containing leather grinding ash, ethylhexyl palmitate, tertiary glycidyl carbonate, a cation fixing agent, a starch waterproofing agent and a priming paint for alkali-resistant seal;
the preparation method of the modified chrome-containing leather ash comprises the following steps: 100g of chrome-containing leather grinding ash is crushed into millimeter size, then is uniformly mixed with 2-4 g of oxalic acid and 120-130 g of water, is stirred and adjusted to pH 4-4.5, 0.3-2.1 g of sodium citrate dihydrate and 3-6 g of chrome fixing agent are added, stirring is carried out for 2 hours at 45 ℃, and after continuous stirring, the modified chrome-containing leather ash is obtained;
the preparation method of the chromium fixing agent comprises the following steps: stirring and dispersing 20g of 2-acrylamide-2-methylpropanesulfonic acid, 12-15 g of ethyl acetoacetate and 10g of water at 50-60 ℃, sequentially adding 12-25 g of methacryloyloxyethyl trimethyl ammonium chloride, 0.6-0.9 g of ethylenediamine tetraacetic acid and 400-500 g of water, adding 2.25-2.7 g of potassium persulfate initiator, stirring and reacting for 1-2h at 70-80 ℃, then adding 1.6-2.7 g of aluminum hydroxy oxalate, adjusting the pH value to 7.5, carrying out heat preservation and reacting for 1-2h, and carrying out vacuum drying to obtain the chromium fixing agent.
2. The method for preparing artificial stone using chrome-containing leather ash according to claim 1, wherein the method for preparing artificial stone according to claim 1 comprises the steps of:
(1) Uniformly stirring 42.5-grade cement, calcium chloride, ethylhexyl palmitate, versatic acid glycidyl ester, and the dried modified chrome-containing leather ash obtained by the method in claim 1, wherein the weight ratio of the modified chrome-containing leather ash, the 42.5-grade cement, the calcium chloride, the ethylhexyl palmitate, the versatic acid glycidyl ester, the cationic fixing agent, the starch waterproof agent and the water is as follows: 100: (595-775): (3-8): (1-2): (2-3): (1-2): (2-3): (800-1000), continuing stirring, pouring into a mold, defoaming, and trowelling the surface;
(2) And (3) treating a base material: removing dust, grease, mould algae and other adherents on the painted surface, keeping the surface clean, dry and firm, and keeping the water content of the wall surface less than 10% and the pH value less than 10;
(3) Leveling the wall surface: leveling the wall surface by using matched plastering mortar, wherein the time is usually 2-3 times, scraping special putty powder, and polishing the surface, and cleaning floating dust;
(4) Spraying the true stone surface in the step (3), and brushing with alkali-resistant seal so as to control the base coat on the simulated stone surface to be about 1 mm;
the alkali-resistant seal primer comprises the following components: 180 parts of water, 0.6 part of hydroxyethyl cellulose and 16 parts of HYM-21 rubber powder; 4 parts of propylene glycol; 0.7 parts of wetting agent; 2.7 parts of dispersing agent; 2 parts of defoaming agent; 3 parts of multifunctional auxiliary agent; 38 parts of titanium dioxide; 63 parts of other fillers; 50 parts of quartz sand (120 meshes); 13 parts of film forming auxiliary agent; bade Fu RS-308260 parts; 0.3 part of penetrating agent (penetrating agent JFC-M; alkali swelling thickener 0.4-5 parts, compatilizer 10-20 parts).
3. The method for preparing the simulated stone by using the chrome-containing leather ash according to claim 1, wherein the preparation method of the compatilizer comprises the following steps: the cardanol polyoxyethylene ether BGF-6 is 16g and 1, 4-butanedithiol is 15g, the mixture is stirred and reacts for 1 to 2 hours at 70 to 80 ℃, the temperature is reduced to 40 ℃ to remove the 1, 4-butanedithiol, then DL-panthenol 6.8 g is added, the mixture is reacted for 30 to 60 minutes at 45 ℃, then o-cresolphthalein is added, the mixture is reacted for 1 to 2 hours at 45 ℃, and the pH value is regulated to 7.5, thus obtaining the compatilizer.
4. The method for preparing artificial stone using chrome-containing leather ash according to claim 1, wherein the cation fixing agent is: heating and stirring high-amylose corn starch milk (with the mass fraction of 35%, the pH value of 6.5 and the balance of water) for 20 hours at 65 ℃, then adding propylene oxide with the starch content of 30% for 2 times, adding NaOH (with the dry weight of 2.5% of starch) and Na2SO4 (with the dry weight of 20% of water), reacting for 24 hours at 45 ℃, neutralizing, filtering, washing and drying to obtain hydroxypropyl starch;
b preparing 350mL of acetate buffer solution (the rest is water) by using 25.6g of anhydrous sodium acetate and 11.2mL of acetic acid, dissolving 15g of hydroxypropyl starch in the acetate buffer solution at 60 ℃, adding 1.3mL of propargylamine under stirring, adding 0.3g of sodium cyanoborohydride each time for 12 hours, stirring the mixture at 50 ℃ for 32 hours, dialyzing for 24 hours, concentrating the solution by a rotary evaporator after dialysis, and drying in vacuum for 24 hours to obtain the terminal alkyne starch; 20mL of N, N-dimethylformamide is mixed with 40mL of water, 6g of terminal alkyne starch and 260mg of 3-azidopropylamine are dissolved in the mixed solution, 45mg of copper sulfate pentahydrate and 45mg of sodium ascorbate are added, the solution is stirred for 12 hours at 80 ℃, the product is dissolved in a mixture of 20mL of dichloromethane and 20mL of trifluoroacetic acid for deprotection (stirring is carried out for 6 hours at room temperature under the condition of N2 connection), and then the solution is dialyzed for 48 hours and dried to obtain the terminal cationic starch.
5. The method for preparing artificial stone using chrome-containing leather ash according to claim 1, wherein the starch waterproof agent is: respectively weighing 16g of hydroxypropyl starch and 14-17 g of terminal cationic starch, preparing a suspension with the concentration of 6% by deionized water, and placing the suspension in a three-neck flask; mechanically stirring, heating and preserving heat for 2 hours in a constant-temperature water bath at 98 ℃ to obtain membrane liquid; 3g of hydroxyl silicone oil (the mass ratio of the curing agent is 15:1) is dissolved in 50mL of ethyl acetate to be mixed with the film liquid, the mixture is stirred and reacted for 1 to 2 hours at the temperature of 70 to 80 ℃, then 6g of water, 3 to 4g of coupling agent and 0.3 to 0.5g of 1- (3-chloropropoxy) -4-fluorobenzene are added, the pH value is adjusted to 10, the mixture is stirred and reacted for 1 to 2 hours at the temperature of 30 to 40 ℃, and the mixture is dried in vacuum to obtain the starch waterproof agent.
6. The method for using chrome-containing leather ash according to claim 1 for simulating stone surfaces,
the coupling agents are KH550 and KH570.
CN202310318178.XA 2023-03-25 2023-03-25 Preparation method for preparing simulated stone by using chrome-containing leather ash Pending CN116332580A (en)

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Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN116808502A (en) * 2023-06-29 2023-09-29 烟台大学 Preparation and application of chromium-removing ammonia-reducing agent for chromium-containing collagen liquid extracted from waste leather scraps

Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN116808502A (en) * 2023-06-29 2023-09-29 烟台大学 Preparation and application of chromium-removing ammonia-reducing agent for chromium-containing collagen liquid extracted from waste leather scraps
CN116808502B (en) * 2023-06-29 2024-03-19 烟台大学 Preparation and application of chromium-removing ammonia-reducing agent for chromium-containing collagen liquid extracted from waste leather scraps

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